Tonight's Nationals start Tony Armas has never hit more than 2 batters in a game, but tomorrow's starter Livan Hernandez tied the modern record for hitting batters last July when he plunked 4 Colorado Rockies in a single game. Hernandez is the 10th pitcher to hit 4 batters in a game since Craig Biggio's career began. Of those 10 games, Biggio played in 3, but surprisingly has never been plunked himself in any of them.
On June 2, 1996 Darryl Kile hit 4 Cardinals batters while pitching for the Astros. The following year, on September 13, 1997, Tom Candiotti, pitching for the Dodgers, hit the Astro's Darryl Kile, Tony Eusebio, and Derrick Bell twice but somehow missed Biggio. On April 19, 2000, Orel Hershisher, also pitching for the Dodgers against the Astros, hit Shane Reynolds, Jeff Bagwell and Richard Hidalgo twice. Hidalgo also got hit one other time in that game, tying the record for batters being hit in a game with 3. Craig Biggio has never been hit more than twice in a game.
Of the 10 pitchers who have hit 4 batters in a game, 5 have hit Craig Biggio with a pitch (on another occasion) - Pedro Astacio (7), Darryl Kile (1), Orel Hershiser (3), James Baldwin (1), and Tom Candiotti (1). Livan Hernandez joins Scott Schoeneweis, Victor Zambrano, Omar Olivares, and Steve Sparks as pitchers who hit 4 batters during the Biggio era but have never plunked Biggio.
Retrosheet lists all the 4 plunk games since 1960 on this page, but there is a whole lot of other stuff there too, so you'll need to search a bit.